Cosmetic use of selected polyamino polymers as antioxidants

ABSTRACT

Use of a polyamino polymer to inhibit the light-induced peroxidation of lipids, particularly inhibition of the photo-peroxidation of lipids induced by nanopigments. The invention also relates to the use of a polyamino polymer to inhibit the light-induced peroxidation of proteins. This property of polyamino polymers finds applications in particular in the cosmetics, pharmaceutical, veterinary and agrifood fields.

[0001] Applicants reference herein the patent applications of BOUDIAFBOUSSOUIRA and DIDIER CANDAU for COMPOSITION COMPRISING ADIBENZOYLMETHANE DERIVATIVE AND A POLYAMINO POLYMER(Docket No.05725.0304), and of BOUDIAF BOUSSOUIRA and DIDIER CANDAU for COMPOSITIONCOMPRISING A CINNAMIC ACID DERIVATIVE AND A POLYAMINO POLYMER (DocketNo. 05725.0305), filed on even date herewith and incorporate thedisclosures thereof specifically by reference herein.

[0002] The present invention relates to the use of a polyamino polymeras an antioxidant. The invention relates in particular to the use of apolyamino polymer in order to inhibit the light-induced peroxidation oflipids. This invention relates in particular to inhibition of thelight-induced peroxidation of lipids of sebaceous origin (sebum), suchas squalene, as well as to the light-induced peroxidation (orphoto-peroxidation) of plant oils. The invention relates particularly toinhibition of the photo-peroxidation of lipids induced by nanopigments.The invention also relates to the use of a polyamino polymer in order toinhibit the light-induced peroxidation of proteins. This inventionrelates in particular to inhibition of the light-induced peroxidation ofproteins of the skin, such as collagen, as well as to inhibition of thelight-induced peroxidation (or photo-peroxidation) of proteins of animalor plant origin and derivatives thereof. This property of the polyaminopolymers finds applications in particular in the cosmetic,pharmaceutical, veterinary and agrifood fields.

[0003] It is known that lipids found at the surface of the skin, thescalp and the hair are permanently subjected to external attack and inparticular to air, atmospheric pollutants, visible radiation andespecially ultraviolet (UV) radiation.

[0004] These lipids are both those which form part of the constituentsof the skin or of the hair and those which are secreted by the skin,including the scalp, and/or those which are deposited on the skin or thehair during the application onto the latter of products containinglipids.

[0005] The lipids most exposed to external attack are those contained inthe greasy secretions of the skin such as sebum, which is rich insqualene. The presence of six double bonds in squalene molecules makesthese molecules sensitive to oxidation phenomena. Thus, during prolongedexposure to UV, squalene photo-peroxidizes to give squalene peroxides.

[0006] This high production of squalene peroxides results in particularin a series of chain degradations, in particular in and on the skin,giving rise to many skin disorders. Thus, these squalene peroxides areinvolved in particular in:

[0007] the pathogenesis of acne, as described by Saint Léger et al. (seeBritish Journal of Dermatology, 1986: 114, pp. 535-542), who point outthat squalene peroxides are comedogenic;

[0008] premature ageing of the skin as described by Keiko O. H. Sawa etal. (see The Journal of Toxicology Sciences, 1984: 19, pp. 151-159) whodiscuss the consequences of skin bums caused by the sun;

[0009] irritation phenomena as reported by Takayoshi Tanaka et al. (seeJ. Clin. Biochem. Nutr., 1986: 1, pp. 201-207), who report the damagecaused in particular by the repeated use of certain shampoos;

[0010] the production of malodorous volatile products (aldehydes,ketones, acids, etc.) and, lastly, in

[0011] immunosuppression, as biochemical messengers of the biologicaleffects of UV irradiation of the skin, as described by M. Picardo et al.(see Photodermatol. Photoimmunol. Photomed., 1991: 8, pp. 105-110).

[0012] It is known that the proteins found at the surface of the skin,the scalp and the hair are also subjected to external attack and inparticular to the air, atmospheric pollutants and visible radiation andespecially ultraviolet (UV) radiation. In this respect, mention may bemade of the following documents: M. -L. Hu and A. L. Tappel, Photochem.Photobiol. 56 (3), 357-363, 1992; M. J. Davies et al., Biochem. J., 305,643-649, 1995.

[0013] These proteins are both those which form part of the constituentsof the skin or the hair and those which are secreted by the skin,including the scalp, and/or those which are deposited on the skin or thehair during application onto the latter of products containing proteinsor protein derivatives.

[0014] Among the proteins most exposed to external attack, mention maybe made in particular of collagen, glycoproteins and skin enzymes.

[0015] In order to limit the peroxidation of unsaturated lipids andproteins, it is known to apply to the skin photoprotective compositionscontaining at least one anti-free-radical agent or at least onescreening agent.

[0016] Among the screening agents, nanopigments of metal oxides,particularly titanium dioxides, are increasingly used in skin and hairproducts on account of their properties of scattering and reflectingultraviolet radiation. When used alone, they allow good protection to beobtained against ultraviolet rays. When combined with low concentrationsof organic screening agents, they lead to the production of highlyprotective products.

[0017] However, light-irradiation of compositions containing metal oxidenanopigments catalyses the oxidation of oxidation-sensitive organiccompounds, in particular:

[0018] lipids of sebaceous origin (even though an overall protectiveeffect of the nanopigments towards lipids of sebaceous origin isobserved on account of their screening activity),

[0019] lipids used in cosmetic formulations,

[0020] proteins of the skin,

[0021] proteins and protein derivatives used in cosmetic formulations.

[0022] An instability to light of compositions containing metal oxidenanopigments is also observed, manifested in particular, for titaniumoxides, in the appearance of a blue-grey colour in the cosmetic productswhen they come into contact with daylight, this also being known asphoto-blueing.

[0023] The inventors have demonstrated, according to the “head space”method, that, when exposed to ultraviolet radiation or after a few hoursat 37° C., titanium oxide catalyses the production of peroxide radicalsfrom the lipid constituents contained in the cosmetic compositions. Thisresults—when these compositions are applied to the skin—in harmfuleffects such as inflammation. For a description of this method,reference may be made in particular to the articles by N'Guyen Q. L. etal. Symposium of AFECG-SFC, Bordeaux, May 1984, pp. 358-359, Evaluationof aldehydic oxidation in cosmetic products; and Warner K. et al.,Journal of Food Science, 1974, V39, pp. 761-765, “Pentane formation andrancidity in vegetable oils”, the disclosures of which are specificallyincorporated by reference herein.

[0024] Faced with these drawbacks, surface-treated pigments haveappeared on the market, this treatment having the effect of limiting thephenomenon of light-induced activity. Thus, patent application WO90/09777 proposes to treat titanium oxide nanopigments with phosphateanions. Patent application JP 03-183,620 describes zinc oxidenanopigments treated with a combination of alumina and silica. Thesesurface treatments aimed at reducing the photocatalytic activity are,however, not satisfactory and the reduction of the phenomenon remainsinsufficient.

[0025] Thus, the compositions known to date provide insufficientprotection, or even no protection at all, of the skin against theperoxidation of skin lipids and proteins and against the peroxidation oflipids and proteins contained in the cosmetic compositions intended tobe applied to the skin.

[0026] The inventors have now discovered that certain polyamino polymershave antioxidant properties and allow the abovementioned problems to besolved.

[0027] The subject of the invention is the use of a polyamino polymer asan antioxidant. For the purposes of the present invention, the termpolyamino polymer is understood to refer to a polymer selected from:

[0028] (A) a polyalkylenepolyamine, or one of its derivatives, selectedfrom:

[0029] (i) polyalkylenepolyamines;

[0030] (ii) alkyl derivatives of polyalkylenepolyamines (A)(i);

[0031] (iii) addition products of alkylcarboxylic acids withpolyalkylenepolyamines (A)(i);

[0032] (iv) addition products of ketones and aldehydes withpolyalkylenepolyamines (A)(i);

[0033] (v) addition products of isocyanates and isothiocyanates withpolyalkylenepolyamines (A)(i);

[0034] (vi) addition products of alkylene oxide or of polyalkylene oxideblock polymers with polyalkylenepolyamines (A)(i);

[0035] (vii) quaternized derivatives of polyalkylenepolyamines (A)(i);

[0036] (viii) addition products of a silicone withpolyalkylenepolyamines (A)(i);

[0037] (ix) copolymers of dicarboxylic acid and ofpolyalkylenepolyamines (A)(i);

[0038] (B) polyvinylimidazoles;

[0039] (C) polyvinylpyridines;

[0040] (D) addition products of 1-vinylimidazole monomers of formula(I):

[0041]  in which:

[0042] radicals R independently represent H or a linear or cyclic,saturated or unsaturated C₁-C₆ alkyl radical,

[0043] n is an integer ranging from 1 to 3, with polyalkylenepolyamines(A)(i) to (A)(ix);

[0044] (E) polymers based on amino acids with a basic side chain; and

[0045] (F) crosslinked derivatives of the polymers (A)(i) to (A)(ix),(B), (C), (D) and (E).

[0046] The polyamino polymers which can be used in the present inventioncan be in the linear, hyperbranched or in dendrimer form.

[0047] Hyperbranched polymers are molecular constructions having abranched structure, generally about a core. Their structure generallylacks symmetry: the monomer or base units involved in the constructionof the hyperbranched polymer can be of varied nature and they aredistributed non-uniformly. The branches in the polymer can be of variednature and length. The number of base units, or monomers, can bedifferent according to the different branching. While remainingasymmetrical, the hyperbranched polymers can have: an extremely branchedstructure, around a core; successive generations or layers of branching;a layer of end chains.

[0048] Hyperbranched polymers are generally obtained from thepolycondensation of one or more monomers ABx, A and B being reactivegroups capable of reacting together, x being an integer greater than orequal to 2, but other preparation processes can be envisaged.Hyperbranched polymers are characterized by their degree ofpolymerization DP=1−b, b being the percentage of non-terminal functionalgroups in B which have not reacted with a group A. Since thecondensation is non-systematic, in contrast with the synthesis ofdendrimers, the degree of polymerization is less than 100%. Usually, bythe known synthetic methods, DP is between 15 and 90%. An end group Tcan be reacted with the hyperbranched polymer to obtain a specificfunctional group at the end of the chains.

[0049] Such polymers are described in particular in B. I. Voit, ActaPolymer, 46, 87-99 (1995); EP-682,059; WO-96/14346; WO-96/14345;WO-96/12754, the disclosures of which are specifically incorporated byreference herein.

[0050] Several hyperbranched polymers can be combined, by means of acovalent bond or another type of bonding, via their end groups. Suchso-called “bridged” polymers come within the definition of thehyperbranched polymers according to the present invention.

[0051] Dendrimers are highly branched polymers and oligomers that arealso known; they have a well-defined chemical structure and are said tobe “perfect” hyperbranched polymers. As a general rule, dendrimerscomprise a core, a determined number of generations of branches, orspindles, and terminal groups. The generations of spindles consist ofstructural units which are identical for the same generation of spindlesand which can be identical or different for different generations ofspindles. The generations of spindles extend radially in a geometricalprogression from the core. The terminal groups of a dendrimer of theN^(th) generation are the terminal functional groups of the spindles ofthe N^(th) generation or terminal generation. Such polymers aredescribed in particular in D. A. Tomalia, A. M. Naylor and W. A. GoddardIII, Angewandte Chemie, Int. Ed. Engl. 29, 138-175 (1990); C. J. Hawkerand J. M. J. Frechet, J. Am. Chem. Soc., 112, 7638 (1990); B. I. Voit,Acta Polymer, 46, 87-99 (1995); N. Ardoin and D. Astruc. Bull. Soc.Chim. Fr. 132, 875-909 (1995), the disclosures of which are specificallyincorporated by reference herein.

[0052] Dendrimers can also, more particularly, be defined by the formula(DI) below:

C[A₁B₁(A₂B₂( . . . (A_(n−1)B_(n−1)(A_(n)B_(n)(T)r_(n))r_(n−1))r_(n−2) .. . )r₂)r₁]s   (DI)

[0053] in which:

[0054] C represents the core, linked by a number s of functional groupsto s spindles A₁B₁ via the groups A₁;

[0055] s is an integer greater than or equal to 1 and less than or equalto the number of functional groups in C;

[0056] the index i (i=1, 2 . . . n) is an integer which denotes thegeneration of each spindle;

[0057] r_(i) (i=1, 2 . . . n−1) represents the number of functionalgroups in the group B_(i) belonging to the spindle (A_(i)B_(i)), ribeing an integer greater than or equal to 2;

[0058] for each spindle (A_(i)B_(i)) (i=1, 2 . . . n), the group B_(i)is linked to r_(i) groups A_(i+1) of a spindle (A_(i+1)B_(i+1));

[0059] each group A_(i) (i≧2) is linked to a single group B_(i−1) of thespindle (A_(i−1)B_(i−1));

[0060] the spindle of n^(th) generation A_(n)B_(n) is linked chemicallyto a number r_(n) of terminal groups T, r_(n) being an integer greaterthan or equal to zero.

[0061] The dendrimer definition given above includes moleculescontaining symmetrical branching; it also includes molecules containingnon-symmetrical branching such as, for example, dendrimers whosespindles are lysine groups, in which the branching of one generation ofspindles onto the preceding generation takes place on the amines α and εof lysine, which leads to a difference in the length of the spindles ofthe different branchings.

[0062] Dense star polymers, starburst polymers and rod-shaped dendrimersare included in the present definition of dendrimers. The moleculesknown as arborols and cascade molecules also fall within the definitionof dendrimers according to the present invention.

[0063] Several dendrimers can be combined together, via a covalent bondor another type of bond, via their terminal groups in order to givespecies known as “bridged dendrimers” or “dendrimer aggregates”. Suchspecies are included in the definition of dendrimers according to thepresent invention.

[0064] Dendrimers can be in the form of a set of molecules of the samegeneration, these being so-called monodispersed sets; they can also bein the form of sets of different generations, which are known aspolydispersed sets. The definition of dendrimers according to thepresent invention includes monodispersed sets as well as polydispersedsets of dendrimers.

[0065] Reference may be made to the following documents, in whichdendrimers containing amine functional groups are described, the contentof these documents being incorporated by reference into the presentdescription: U.S. Pat. No. 4,694,064; U.S. Pat. No. 4,631,337;WO-A-95/02008; WO-A-93/14147; U.S. Pat. No. 4,360,646; Proc. Natl. Acad.Sci. USA, 85, 5409-5413 (1988), the disclosures of which arespecifically incorporated by reference herein.

[0066] The hyperbranched polymers and dendrimers containing aminefunctional groups can also consist of a core and generations of base,monomer or spindle units, of any nature, on which a terminal group Tbearing an amine function has been grafted.

[0067] The polyamino polymers (A)(i) to (A)(ix), (B), (C), (D), (E) and(F) of the invention will be described in greater detail:

[0068] (A)(i)

[0069] The polyalkylenepolyamines preferably used according to theinvention are polymers containing from 7 to 20,000 repeating units.Preferably, polyalkylenepolyamines comprising at least 5% of tertiaryamines, advantageously at least 10% of tertiary amine functions and evenmore preferably at least 20%, are selected. These polymers can be linearor branched homopolymers or copolymers, or dendrimer structures.

[0070] These polymers comprise the following repeating units:

[0071] in which:

[0072] i represents an integer greater than or equal to 2, preferablyi=2;

[0073] n represents an integer

[0074] R represents H or a unit

[0075]  in which j represents an integer greater than or equal to 2,preferably j=2;

[0076] Among the products of the polyalkylenepolyamine family, alsoknown as polyaziridines, mention may be made in particular of:

[0077] Polyethyleneimine, which is a hyperbranched polymer which is wellknown to those skilled in the art: on the subject of polyethyleneimine,reference may be made in particular to the documents: “Kirk-OthmerEncyclopedia of Chemical Technology”, 3rd Edition, Vol. 20, 1982, pp.214-216, and “Polyethyleneimine Prospective Application”, H. N.Feigenbaum, Cosmetic & Toiletries, 108, 1993, p. 73, the disclosures ofwhich are specifically incorporated by reference herein.Polyethyleneimine is commercially available from the company BASF underthe trade names LUPASOL and POLYIMIN; polyethyleneimine is usuallywithin an average molecular weight range from 500 to 2,000,000;

[0078] Polyethyleneimines and polypropyleneimines in the form ofdendrimers are also known, these being manufactured by the company DSM.Patent applications WO 95/02008 and WO 93/14147, the disclosures ofwhich are specifically incorporated by reference herein, describepolyalkylenepolyamines of the dendrimer family, as well as a process fortheir preparation.

[0079] (A)(ii) The alkyl derivatives of polyalkylene-polyamine areproducts that are well known to those skilled in the art. They areobtained in a known manner by alkylation, in aqueous or alcoholicmedium, in the presence of an alkylating agent, preferably in thepresence of NaOH, KOH or carbonate, at temperatures preferably rangingfrom 40° C. to 130° C. The alkylating agent can be selected, forexample, from C₁-C₈ alkyl halide or alkyl sulphate derivatives such as,for example, dimethyl sulphate, diethyl sulphate, butyl bromide, hexylbromide, 2-ethylhexyl bromide, n-octyl bromide or the correspondingchlorides. Reference may be made, for example, to DE-3,743,744 whichdescribes the preparation of such products, the disclosure of which isspecifically incorporated by reference herein.

[0080] (A)(iii) The addition products of alkylcarboxylic acids withpolyalkylenepolyamines are products that are known to those skilled inthe art and whose preparation is described, for example, in patentapplications WO 94114873; WO 94/20681; WO 94/12560, the disclosures ofwhich are specifically incorporated by reference herein. The addition ofalkylcarboxylic acids to polyalkylenepolyamines can be carried out byreacting, in a known manner, an acid, an amide, an ester or an acidhalide with the polyalkylenepolyamine polymer.

[0081] The addition products of alkylcarboxylic acids withpolyalkylenepolyamines can be, for example, the addition products ofsaturated or unsaturated, linear or branched C₂-C₃₀ alkylcarboxylicacids with a polyethyleneimine. Among the carboxylic acids which can beused, mention may be made, for example, of acetic acid, propionic acid,butyric acid, 2-ethylhexanoic acid, benzoic acid, lauric acid, myristicacid, palmitic acid, stearic acid, oleic acid, linoleic acid,arachidonic acid and behenic acid, as well as mixtures of fattysubstances such as, for example, mixtures of fatty esters available inthe form of natural products, and among which mention may be made of:coconut oil, soybean oil, linseed oil, rapeseed oil, etc.

[0082] (A)(iv) The addition products of ketones and aldehydes withpolyalkylenepolyamines (A)(i) can be prepared by processes known tothose skilled in the art and lead to the production of α-hydroxyamineunits;

[0083] (A)(v) The addition products of isocyanates and isothiocyanateswith polyalkylenepolyamines (A)(i) can be prepared by processes known tothose skilled in the art and lead to the production of urea and thioureaunits;

[0084] (A)(vi) The addition products of alkylene oxide and ofpolyalkylene oxide block polymers with polyalkylenepolyamines (A)(i) canbe prepared by processes known to those skilled in the art; referencemay be made, for example, to the documents EP-541,018 and U.S. Pat. No.4,144,123, the disclosures of which are specifically incorporated byreference herein, in which such molecules are described; ethoxylatedpolyethyleneimine derivatives are commercially available under thetradename: LUPASOL 61 (BASF);

[0085] (A)(vii) The quaternized derivatives of polyalkylenepolyamines(A)(i) can be prepared by processes known to those skilled in the art;

[0086] (A)(viii) The addition products of a silicone withpolyalkylenepolyamines (A)(i) are, for example, polyethyleneiminesgrafted with polydimethylsiloxane units, the preparation of which isdescribed in the document U.S. Pat. No. 5,556,616, the disclosure ofwhich is specifically incorporated by reference herein, and sold by thecompany Macintyre under the trade name MACKAMER PAVS;

[0087] (A)(ix) The copolymers of dicarboxylic acid and ofpolyalkylenepolyamines (A)(i) can be prepared by polycondensation ofdicarboxylic acids with polyalkylenepolyamines.

[0088] Among the dicarboxylic acids which can be used to preparepolyamidoamines, mention may be made of C₂ to C₁₀ dicarboxylic acidssuch as, for example, oxalic acid, malonic acid, itaconic acid, succinicacid, maleic acid, adipic acid, glutaric acid, sebacic acid,terephthalic acid and orthophthalic acid, as well as mixtures thereof.

[0089] The polyalkylenepolyamines used to prepare the polyamidoaminesare advantageously selected from those having from 3 to 10 nitrogenatoms, such as, for example, diethylenetriamine, triethylenetetramine,dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine,aminopropylethylenediamine and bisaminopropylethylenediamine, as well asmixtures thereof. Polyethyleneimines such as those described above forthe preparation of polyamidoamines can also be used.

[0090] Such compounds are described, for example, in the documents U.S.Pat. No. 4,144,423 and WO 94129422, the disclosures of which arespecifically incorporated by reference herein.

[0091] (B)

[0092] The term polyvinylimidazole comprises polyvinylimidazole (PVI)homopolymers and copolymers obtained by radical polymerization ofvinylimidazole monomers of the following structure:

[0093] The copolymers can be, for example, vinylimidazole copolymerscontaining at least 5% of vinylimidazole units with monomers selectedfrom vinylpyrrolidinone, acrylic acid and acrylamide units. Thesynthesis of such compounds is well known to those skilled in the art;on this subject, reference may be made in particular to the documents:J. Am. Chem. Soc., Vol. 85, 1962, p. 951; Polymer Letters Ed., Vol. 11,1973, p. 465-469; Macromolecules, Vol. 6(2), 1973, p. 163-168; Ann. N.Y.Acad. Sci., Vol. 155, 1969, p. 431; FR-A-1,477,147; JP-69 07395; J.Macromol. Scien. Chem., Vol. A21(2), 1984, p. 253, the disclosures ofwhich are specifically incorporated by reference herein.

[0094] (C)

[0095] The term polyvinylpyridine comprises vinylpyridine homopolymersand copolymers obtained by radical polymerization of vinylpyridinemonomers (substituted in position 2 or 4 of the pyridine ring) of thefollowing structure:

[0096] The copolymers can be, for example, vinylpyridine copolymerscontaining at least 5% of vinylpyridine units with monomers selectedfrom vinylpyrrolidinone, acrylic acid and acrylamide units.

[0097] (D)

[0098] The addition products of 1-vinylimidazole monomers correspondingto formula (I):

[0099] in which the radicals R independently represent H or a saturatedor unsaturated, linear or cyclic, C₁-C₆ alkyl radical,

[0100] n is an integer ranging from 1 to 3, with polyalkylenepolyaminesand their derivatives (A)(i) to (A)(ix).

[0101] Among the derivatives of formula (I) which can be used, mentionmay be made, for example, of 2-methyl-1-vinylimidazole and2-benzyl-1-vinylimidazole.

[0102] These products are known to those skilled in the art: theirpreparation is described, for example, in patent application WO94/29422, the disclosure of which is specifically incorporated byreference herein.

[0103] (E)

[0104] The polymers based on amino acids with a basic side chain arepreferably selected from proteins and peptides comprising at least 5%,advantageously at least 10%, of amino acids selected from histidine,lysine and arginine.

[0105] Among these polymers, mention may be made, for example, ofpolylysines and polyhistadines.

[0106] (F)

[0107] Crosslinked derivatives of the polymers (A)(i) to (A)(ix), (B),(C) and (D). Among the crosslinking agents which can be used, mentionmay be made of halo-hydrin-, glycidyl, aziridino- and isocyanatederivatives; such crosslinking agents, as well as the methods for usingthem, are well known to those skilled in the art. Among the best known,mention may be made of: epichlorohydrin, α,ω-bis(chlorohydrin)polyalkylene glycol ethers, α,ω-dichloroalkanes such as, for example,1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane,1,4-dichlorobutane and 1,6-dichlorohexane; such crosslinking agents andtheir use for crosslinking polyethyleneimine derivatives are describedin WO 94/12560, the disclosure of which is specifically incorporated byreference herein.

[0108] Preferably, in carrying out the present invention, polyaminopolymers comprising at least 5% of tertiary amines, advantageously atleast 10% of tertiary amine functions and even more preferably at least20%, are selected.

[0109] According to the invention, the polyamino polymer isadvantageously selected from:

[0110] (A) (i) hyperbranched polyethyleneimines,

[0111] (ii) alkyl derivatives of polyethyleneimine;

[0112] (iii) addition products of alkylcarboxylic acids withpolyethyleneimine;

[0113] (iv) addition products of ketones and aldehydes withpolyethyleneimine;

[0114] (v) addition products of isocyanates and isothiocyanates withpolyethyleneimine;

[0115] (vi) addition products of alkylene oxide and polyalkylene oxideblock polymers with polyethyleneimine;

[0116] (vii) quaternized derivatives of polyethyleneimine;

[0117] (viii) addition products of a silicone with polyethyleneimine;

[0118] (ix) copolymers of dicarboxylic acid and of polyethyleneimine;

[0119] (B) polyvinylimidazoles.

[0120] Even more preferably, the polyamino polymer is selected from:

[0121] (A) (i) hyperbranched polyethyleneimines; and

[0122] (vi) the addition products of either ethylene oxide or ofpolyethylene oxide block polymers with polyethyleneimine.

[0123] Advantageously, the polyamino polymer is a polyethyleneimine.

[0124] Preferably, polyethyleneimine derivatives comprising at least 5%of tertiary amines, advantageously at least 10% of tertiary aminefunctions and even more preferably at least 20%, are selected.

[0125] Such polymers make it possible to inhibit oxidation reactions ingeneral, irrespective of their origin. In particular, they have theproperty of inhibiting light-induced peroxidation of photo-oxidizablelipids and the light-induced peroxidation of proteins.

[0126] Thus, the subject of the invention is more particularly apolyamino polymer as described above for inhibiting the peroxidation oflipids induced by UV radiation.

[0127] Among the photo-oxidizable lipids to which the invention relates,mention may be made of unsaturated sebum lipids such as squalene, aswell as the photo-oxidizable fatty substances usually used in theformulation of cosmetics.

[0128] The use of the polyamino polymers according to the invention toinhibit the light-induced peroxidation of lipids is particularlynoteworthy when these lipids are in the presence of nanopigments, thesenanopigments having the property of promoting the photo-oxidationreactions.

[0129] Thus, the presence of at least one polyamino polymer in acosmetic composition comprising at least one nanopigment makes itpossible, on application to the skin, to avoid the photo-peroxidation ofthe derivatives of skin sebum.

[0130] In addition, the presence of at least one polyamino polymer in acosmetic composition comprising at least one photo-oxidizable fattysubstance and at least one nanopigment makes it possible, both onstorage and on application to the skin, to avoid the photo-peroxidationof these fatty substances.

[0131] It has also been observed that the polyamino polymers accordingto the invention made it possible to inhibit the photo-peroxidation ofproteins, in particular the photo-peroxidation of proteins which isinduced by nanopigments.

[0132] Thus, the subject of the invention is more particularly the useof a polyamino polymer as described above to inhibit the peroxidation ofproteins induced by UV radiation.

[0133] Among the photo-oxidizable proteins to which the inventionrelates, mention may be made of skin proteins such as collagen, as wellas the photo-oxidizable proteins usually used in the formulation ofcosmetics.

[0134] The use of the polyamino polymers according to the invention toinhibit the light-induced peroxidation of proteins is particularlynoteworthy when these proteins are in the presence of nanopigments,these nanopigments having the property of promoting the photo-oxidationreactions.

[0135] Thus, the presence of at least one polyamino polymer in acosmetic composition comprising at least one nanopigment makes itpossible, on application to the skin, to avoid the photo-peroxidation ofskin collagen derivatives.

[0136] In addition, the presence of at least one polyamino polymer in acosmetic composition comprising at least one protein or a proteinderivative and at least one nanopigment makes it possible, both onstorage and on application to the skin, to avoid the photo-peroxidationof these proteins.

[0137] The subject of the invention is also a cosmetic and/ordermatological composition comprising:

[0138] (i) at least one nanopigment,

[0139] (ii) at least one polyamino polymer.

[0140] The subject of the invention is also a cosmetic and/ordermatological composition comprising:

[0141] (i) at least one nanopigment,

[0142] (ii) at least one polyamino polymer,

[0143] (iii) at least one photo-oxidizable fatty substance.

[0144] The subject of the invention is also a cosmetic and/ordermatological composition comprising:

[0145] (i) at least one nanopigment,

[0146] (ii) at least one polyamino polymer,

[0147] (iii) at least one protein or a protein derivative.

[0148] According to the invention, the term “nanopigment” is understoodto refer to a pigment with an average diameter preferably of less than100 nm and more preferably ranging from 5 to 50 nm.

[0149] More particularly, the nanopigments are based on metal oxides.

[0150] The metal oxides are selected from titanium oxide, zinc oxide,cerium and zirconium oxide, or mixtures thereof.

[0151] The nanopigments can be coated or uncoated.

[0152] The coated pigments are pigments which have undergone one or moresurface treatments of chemical, electronic, mechanochemical and/ormechanical nature with compounds as described, for example, in Cosmetics& Toiletries, February 1990, Vol. 105, p. 53-64, the disclosure of whichis specifically incorporated by reference herein, such as amino acids,beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins,sodium, potassium, zinc, iron or aluminium salts of fatty acids,silicones, proteins (collagen, elastin), alkanolamines, silicon oxides,metal oxides or sodium hexametaphosphate, polyols and perfluoro oils.

[0153] The coated pigments are more particularly titanium oxides coated:

[0154] with silica, such as the product “SUNVEIL” from the companyIkeda,

[0155] with silica and iron oxide, such as the product “Sunveil F” fromthe company Ikeda,

[0156] with silica and alumina, such as the products “MICROTITANIUMDIOXIDE MT 500 SA” and “MICROTITANIUM DIOXIDE MT 100 SA” from thecompany Tayca, “TIOVEIL” from the company Tioxide,

[0157] with alumina, such as the products “TIPAQUE TTO-55 (B)” and“TIPAQUE TTO-55 (A)” from the company Ishihara, and “UVT 14/4” from thecompany Kemira,

[0158] with alumina and aluminium stearate, such as the product “UVTITAN M212” from the company Kemira,

[0159] with alumina and aluminium stearate, such as the product“MICROTITANIUM DIOXIDE MT 100 T” from the company Tayca,

[0160] with alumina and aluminium laurate, such as the product“MICROTITANIUM DIOXIDE MT 100 F” from the company Tayca,

[0161] with zinc oxide and zinc stearate, such as the product “BR 351”from the company Tayca,

[0162] with silica, alumina and silicone, such as the products“MICROTITANIUM DIOXIDE MT SAS” from the company Tayca,

[0163] with silica, alumina and perfluoropolymethyl isopropyl ether,such as the product “TiO₂ VF-25-33” from the company Toshiki,

[0164] with silica, alumina, aluminium stearate and silicone, such asthe product “STT-30-DS” from the company Titan Kogyo,

[0165] with alumina and silicone, such as the products “TIPAQUE TTO-55(S)” from the company Ishihara, and “UV TITAN M262” from the companyKemira,

[0166] with triethanolamine, such as the product “STT-65-S” from thecompany Titan Kogyo,

[0167] with stearic acid, such as the product “TIPAQUE TTO-55 (C)” fromthe company Ishihara,

[0168] with sodium hexametaphosphate, such as the product “MICROTITANIUMDIOXIDE MT 150 W” from the company Tayca.

[0169] Combinations of coated or uncoated titanium oxide nanopigmentswhich are made water-dispersible by a hydrophilic treatment oroil-dispersible by a hydrophobic treatment, such as those described inEuropean Patent Application 456,460, the disclosure of which isspecifically incorporated by reference herein, can also be used.

[0170] Mention may also be made of metal oxide mixtures, in particularmixtures of titanium dioxide and cerium dioxide, including theweight-equivalent silica-coated mixture of titanium dioxide and ceriumdioxide, sold by the company Ikeda under the name “SUNVEIL A”, as wellas the mixture of titanium dioxide and zinc dioxide coated with alumina,silica and silicone, such as the product “M 261” sold by the companyKemira, or coated with alumina, silica and glycerol, such as the product“M 211” sold by the company Kemira.

[0171] The uncoated titanium oxides are sold, for example, by thecompany Tayca under the trade names “MICROTITANIUM DIOXIDE MT 500 B” or“MICROTITANIUM DIOXIDE MT 600 B”, by the company Degussa under the name“P 25”, by the company Wackherr under the name “TRANSPARENT TITANIUMOXIDE PW”, by the company Miyoshi Kasei under the name “UFTR” and by thecompany Tomen under the name “ITS”.

[0172] The uncoated zinc oxides are sold, for example, by the companySumitomo under the name “ULTRA FINE ZINC OXIDE POWDER”, by the companyPresperse under the name “FINEX 25”, by the company Ikeda under the name“MZO-25” or by the company Sunsmart under the name “Z-COTE”.

[0173] The uncoated cerium oxide is sold under the name “COLLOIDALCERIUM OXIDE” by the company Rhône Poulenc.

[0174] According to the invention, the coated or uncoated titanium oxidenanopigments are particularly preferred.

[0175] The concentration of metal oxide nanopigments in the cosmeticcompositions according to the invention preferably ranges from 0.1 to20% by weight relative to the total weight of the composition, and morepreferably from 0.25 to 15%.

[0176] The concentration of polyamino polymers in the cosmeticcompositions according to the invention preferably ranges from 0.05 to10% by weight relative to the total weight of the composition, morepreferably from 0.5 to 5%.

[0177] A person skilled in the art will known how to adjust, by means ofsimple tests, the proportions of polyamino polymer relative to thenanopigment, and optionally relative to the other components of thecomposition, in particular the photo-oxidizable fatty substances and theproteins or protein derivatives. The reason for this is that the optimumproportions of the various constituents can vary, for example, dependingon the molecular weight of the polymer, the amine content and/or thetertiary amine content in this polymer.

[0178] According to the invention, the expression photo-oxidizable fattysubstances is understood to refer to fatty substances comprising alkylchains containing at least one unsaturation, such as, for example, fattyacids, hydroxylated fatty acids, sterols and their derivatives, amongwhich mention may be made of sterol esters, fatty acid esters,glycolipids, phospholipids, ceramides and terpenes.

[0179] The photo-oxidizable fatty substances to which the inventionrelates are those whose iodine value preferably ranges from 5 to 200. Inorder to measure the iodine value, reference may be made to “Iodinevalue: Wij's method, Handbook of Biochem. & Mol. Biol. p. 512”, thedisclosure of which is specifically incorporated by reference herein.This value makes it possible to characterize the susceptibility of thefatty chains to be oxidized.

[0180] The compositions according to the invention advantageouslycomprise from 0.5% to 60% by weight, relative to the total weight of thecomposition, of at least one photo-oxidizable fatty substance.

[0181] It is thus possible to modify the iodine value of each of thecompounds of the fatty phase by means of the content of this ingredientin the fatty phase. The degree of unsaturation C of the fatty phase of acomposition is defined by the formula:$C = {\sum\limits_{i = 1}^{n}\quad {\left\lbrack {V.I.} \right\rbrack i*\left\lbrack {T.H} \right\rbrack i}}$

[0182] in which [V.I.]i is the iodine value of the oil i and [T.H.]i isits weight percentage relative to the total weight of the fatty phase.Advantageously, the degree of unsaturation C of the fatty phase of thecompositions according to the invention preferably ranges from 2.5 to4000 and more preferably from 50 to 4000.

[0183] The invention relates mainly to the plant oils used in cosmetics,the squalene and the cholesterol present on the skin.

[0184] Among the plant oils used in cosmetics, mention may be made moreparticularly of apricot oil, sweet almond oil, groundnut oil, avocadooil, candlenut oil, borage oil, camellia oil, false flax oil, saffloweroil, blackcurrant oil, cereal oil, chayote oil, coconut oil, rapeseedoil, coriander oil, cotton oil, cumin oil, cynara oil, evening primroseoil, perilla oil, cod liver oil, corn germ oil, jojoba oil, kiwi oil,lanolin oil, lychee oil, linseed oil, longan oil, mango oil, hazelnutoil, olive oil, palm oil, passionflower oil, grapeseed oil, cluster pineoil, Italian stone pine oil, pistachio oil, musk rose oil, sesame oil,shorea oil (floor grease), soybean oil, rice bran oil, turtle oil,sunflower oil, whale oil, tea oil, karite butter and vitamin Ftriglycerides.

[0185] The invention also relates to inhibition of thephoto-peroxidation of proteins: this property applies to any type ofprotein, whether it is one of animal or plant origin, and also appliesto protein hydrolysates (peptides, amino acids) and to the productsderived from the condensation of a protein or a protein fragment with: afatty acid, a silicone such as, for example, collagen fibres in sheetform sold by the company Henkel under the trade name POLYMOIST MASKA4-125; bird or fish collagen hydrolysates; hydrolysates of proteinsgrafted with fatty acids, such as the product sold by the company Seppicunder the brand name LIPACIDE; hydrolysates of proteins grafted with apolydimethylsiloxane fragment, for example such as the product sold bythe company Croda under the brand name CRODASONE.

[0186] These compositions afford effective protection against all kindsof oxidative attack without the need for other screening agents, inparticular chemical screening agents. Thus, the risks of intolerance arereduced when compared with compositions containing several screeningagents. In addition, with an equivalent efficacy, the compositionsaccording to the invention are easier to prepare and less expensive thanthose of the prior art.

[0187] The compositions of the invention can be in variouspharmaceutical forms, and in particular in the form of oil-in-water orwater-in-oil emulsions, solutions, gels or vesicular dispersions. Thesecompositions can be a care cream, a milk, a shampoo, a lotion or aserum.

[0188] According to a preferred variant, the compositions of theinvention also comprise at least one complexing agent which makes itpossible to complex the metals which may be present in thesecompositions, and in particular those in the water used in thecomposition, and thus make these metals inactive.

[0189] The complexing agent which can be used in the compositions of theinvention is, for example, a phosphonic acid derivative and is selectedin particular from 3-ethylenediaminetetra(methylenephosphonic) acid,diethylenetriaminepenta(methylenephosphonic acid) and their sodiumsalts. Preferably, the complexing agent is the pentasodium salt ofdiethylenetriaminepenta(methylenephosphonic acid).

[0190] As other complexing agents which neutralize the action of metals,diethylenetriaminepentaacetic acid, sold for example by the companySigma, can also be used.

[0191] The complexing agents, such as ethylenediaminetetraacetic acid(EDTA) which is an iron-chelating agent, have a pro-oxidizing effect andthus cannot be used alone in the compositions of the invention forantioxidant purposes. However, it is possible to use this type of agentin combination, in particular, with a phosphonic acid derivative.

[0192] When it is present, the metal-complexing agent is at aconcentration which is selected preferably from 0.005% to 0.1% by weightrelative to the total weight of the composition.

[0193] The compositions of the invention can moreover contain adjuvants,used alone or as a mixture, and in particular those selected fromsurfactants (emulsifier or co-emulsifier) of nonionic, anionic, cationicor amphoteric type, treating agents, active agents, thickeners,suspending agents, dyes, fragrances, fillers, neutralizers, excipients(oils/water) and preserving agents.

[0194] The composition of the invention can be used as a cosmeticcomposition or for the manufacture of a dermatological composition forprotecting the human epidermis or the hair against ultraviolet rays, asan antisun composition or as a make-up product.

[0195] The adjuvants mentioned can be incorporated at the usual dosescommonly accepted, avoiding, as far as possible, those liable to releaseoxidation-catalysing metals. They can be lipophilic or hydrophilic.

[0196] When the cosmetic composition according to the invention is usedto protect the human epidermis against UV rays or as an antisuncomposition, it can be in the form of a suspension or dispersion insolvents or fatty substances, in the form of a nonionic vesiculardispersion or alternatively in the form of an emulsion such as a creamor a milk or in the form of an ointment, a gel, a solid stick, anaerosol mousse or a spray.

[0197] When the cosmetic composition according to the invention is usedto protect the hair, it can be in the form of a shampoo, a lotion, agel, an emulsion, a nonionic vesicular dispersion or a lacquer for thehair and can constitute, for example, a rinse-out composition, to beapplied before or after shampooing, before or after dyeing or bleaching,before, during or after permanent-waving or straightening the hair, astyling or treating lotion or gel, a blow-drying or hairsetting lotionor gel, or a permanent-waving, straightening, dyeing or bleachingcomposition for the hair.

[0198] When the composition is used as a make-up product for theeyelashes, the eyebrows or the skin, such as an epidermal treatmentcream, a foundation, a tube of lipstick, an eyeshadow, a blusher, amascara or an eyeliner, it can be in solid or pasty, in anhydrous oraqueous form, such as oil-in-water or water-in-oil emulsions, nonionicvesicular dispersions or alternatively suspensions.

[0199] The invention also relates to a use of these compositions ascosmetic compositions or for the manufacture of dermatologicalcompositions intended for treatment to combat and/or prevent irritation,inflammation of the skin, acne and immunosuppression, as well as to theuse of these compositions to combat and/or prevent the signs of ageing.These skin phenomena are induced in particular by solar radiation.

[0200] The invention also relates to a cosmetic treatment process forthe skin to combat and/or prevent ageing, in particular light-inducedageing.

[0201] Another subject of the invention is a process for conservingcompositions containing at least one light-oxidizable lipid.

[0202] On account of the fact that a cosmetic and/or dermatologicalcomposition comprising such a polyamino polymer instantaneously blocksthe initiation of peroxidation reactions in the presence of radiation,such a composition is particularly useful for combating light-inducedskin irritation, or even inflammation, immunosuppression and acne.

[0203] Thus, another subject of the invention is the use of a polyaminopolymer as an antioxidant, in particular in a cosmetic composition orfor the preparation of a dermatological composition intended for thepreventive or curative treatment of irritation, inflammation,immunosuppression and/or acne, in particular irritation, inflammation,immunosuppression and/or acne induced by photo-peroxidation, moreparticularly the photo-peroxidation of squalene and/or collagen.

[0204] The subject of the invention is also a dermatological compositionaccording to the invention, this composition being intended to treat thesigns of ageing of the skin or the hair, in particular the signs ofageing induced by photo-peroxidation, and more particularly the signs ofageing induced by the photo-peroxidation of squalene and/or collagen.

[0205] In the particular case of the treatment of acne, a specificanti-acne agent, an antiseborrhoeic agent and/or an antibacterial agent,and in particular piroctone olamine, sold under the name OCTOPIROX bythe company Hoechst, can also advantageously be incorporated into thecomposition of the invention.

[0206] The subject of the invention is also a cosmetic treatment processwhich involves combating or preventing the signs of ageing by topicalapplication, to the skin and/or the scalp and/or the hair, of acomposition comprising at least one polyamino polymer according to theinvention. The subject of the invention is, in particular, a cosmetictreatment process which involves combating or preventing the signs ofageing induced by photo-peroxidation, and more particularly the signs ofageing induced by the photo-peroxidation of squalene and/or collagen, bytopical application to the skin and/or the scalp and/or the hair of acomposition comprising at least one polyamino polymer according to theinvention.

[0207] On account of its beneficial properties, the composition of theinvention is suitable for protecting any skin type and more especiallygreasy skin and so-called sensitive skin. It can also be used to protectthe lips from cracking.

[0208] In parallel with the topical treatment, the composition of theinvention can be used to conserve compositions containing at least onelight-oxidizable lipid.

[0209] Thus, another subject of the invention is a process forconserving cosmetic, agrifood and/or pharmaceutical compositionscontaining at least one photo-oxidizable lipid or protein or proteinderivative, this process involving incorporating a polyamino polymer asdefined above into the said compositions.

[0210] According to the invention, the composition presents no knownrisks of intolerance and can be used in total safety, in particular inthe cosmetic, dermatological or even veterinary fields.

[0211]FIG. 1 illustrates the effect of polyethyleneimine on thephoto-peroxidation of collagen. The percentages of polyethyleneimine (byweight relative to the total weight of the composition) in thecomposition subjected to the test are represented on the x-axis. Theamounts of collagen peroxides (in picomole equivalents of H₂O₂) assayedin the composition are represented on the y-axis.

[0212] Other characteristics and advantages of the composition of theinvention will emerge more clearly from the description, the examplesand counter-examples which follow, which are given by way ofnon-limiting illustration. In these examples and counter-examples, thepercentages are given on a weight basis.

TESTS

[0213] In the tests described below, polyethyleneimine (PEI) ofmolecular weight 700, sold by the company Aldrich was used.

Test 1

[0214] EX-VIVO Test of Inhibition of the Photo-Peroxidation of Sebum byPolyethyleneimine Under UVA

[0215] Two circular filters of 17 cm² were applied to the forehead of anindividual for 10 min in order to extract a film of sebum. A thin filmof placebo product (formula A) was placed on one of the filters in aproportion of about 3 mg/cm². The product containing polyethyleneimine(products B to D) was applied to the second filter. The filters werethen irradiated with 5 joules UVA/cm² using a Biotronic 360 machine.

[0216] The surface lipids and the peroxides were extracted from thefilters using 5 ml of HPLC-grade acetonitrile, in order to assay:

[0217] the squalene peroxides by HPLC-chemiluminescence afterpost-column reaction with microperoxidase-isoluminol (specific forhydroperoxides);

[0218] the residual squalene by light-scattering HPLC.

[0219] The results are expressed in terms of inhibition of theperoxidation of squalene:${\% \quad {inhibition}} = {\frac{{{SQOOH}\left( {{formula}A} \right)} - {{SQOOH}\left( {{formula}X} \right)}}{{SQOOH}\left( {{formula}A} \right)} \times 100}$

[0220]  with:

[0221] X=B,C,D;

[0222] SQOOH represents the percentage of squalene peroxides relative tothe percentage of squalene (expressed in picomoles of peroxides as H₂O₂equivalent per pg of squalene). Formulae A and X=B, C, D are formulae ofthe following compositions: CTFA name Formula A Formula B Formula CFormula D Cetyl alcohol  5%   5%   5%  5% Glyceryl stearate  3%   3%  3%  3% PEG-50 stearate  3%   3%   3%  3% Mineral oil 20%  20%  20% 20%Caprylic/capric  3%   3%   3%  3% triglycerides Water QSP 100 QSP 100QSP 100 QSP 100 Polyethyleneimine  0% 0.2% 0.5%  1%

[0223] The following inhibition results were obtained: FormulaInhibition of peroxidation A  0% B 40% C 76% D 84%

Test 2

[0224] Inhibition, by Polyethyleneimine, of the Photo-Oxidation ofVitamin F Under UVA Induced by Light-Reactive TiO₂ Nanopigments

[0225] Test principle: compositions (A′, B′, C′) comprising vitamin F,jojoba oil and TiO₂ and optionally polyethyleneimine were spread onto afilter. Photo-oxidative degradation of the vitamin F and the jojoba oilwas initiated under the joint action of the TiO₂ nanopigments and anirradiation with UVA of 100 joules per cm², using a Suntest Hereaus CPSmachine. This degradation lead to the formation of pentane which wasused as a marker for this oxidation. Formation of pentane was measuredby chromatography using a Head-Space-40 machine (sold by the companyPerkin-Elmer). The action of the PEI on the formation of pentane wasthus monitored.

[0226] The compositions of the formulae were as follows: CTFA nameFormula A′ Formula B′ Formula C′ Cetearyl alcohol 4% 4% 4% Ceteareth-331% 1% 1% Glyceryl stearate 1% 1% 1% Cetyl alcohol 1% 1% 1% Jojoba oil 6%6% 6% Vitamin F 6% 6% 6% TiO₂ P25 from Degussa 0% 5% 5% PEI 0% 0% 2%Water QS 100%

[0227] The following results were obtained: Formula Pentane (in ppm)Formula A′ 9 Formula B′ 53 Formula C′ 10

[0228] Formula C′ inhibited the formation of pentane with an efficacy ofabout 80% relative to formula B′. It was almost equivalent to thecontrol (formula A′) which contained no nanopigments, this correspondingto a 97% inhibition of the oxidative phenomenon which can be attributedto the action of the nanopigments.

Test 3

[0229] Inhibition of the Photo-Peroxidation of Collagen byPolyethyleneimine Under UVA

[0230] Test Principle:

[0231] This test makes it possible to evaluate the formation of peroxideresidues in collagen fibres under UVA irradiation (365 nm). The collagen(collagen sheets sold by the company Henkel under the brand namePOLYMOIST MASK) was irradiated using a programmable radiometer(Biotronic UV sold by the company Vilbert Lourmat, fitted with 3 40W/365 nm low-pressure mercury vapour lamps).

[0232] The peroxides formed were measured by chemiluminescence by meansof a photon-counter camera (CCD camera sold by the company Hamamatsu):

[0233] The peroxides were decomposed by an enzyme, microperoxidase(MICROPEROXIDASE MP 11 10 H₂O sold by the company Sigma). During thisreaction, oxygenated active species were produced and reacted with6-amino-2,3-dihydro-1,4-phthalazinedione (ISOLUMINOL, sold by thecompany Sigma) which was also present in the reaction medium. It watsafter this reaction that the isoluminol emitted photons while becomingdeactivated. The photons emitted were counted by the camera; theirnumber was proportional to the amount of peroxides initially present.

[0234] Test Formulae: Formula I CTFA name (placebo) Formula 2 Formula 3Formula 4 Cetyl alcohol  5%   5%  5%  5% Glyceryl stearate  3%   3%  3% 3% PEG-50 stearate  3%   3%  3%  3% Mineral oil 20%  20% 20% 20%Caprylic/capric  3%   3%  3%  3% triglycerides Water QSP 100 QSP 100 QSP100 QSP 100 Polyethyleneimine  0% 0.5%  1%  2%

[0235] Method of Operation:

[0236] Preparation of the chemiluminescence reaction mixture:

[0237]34.8 mg of Isoluminol are weighed out and were dissolved, withmagnetic stirring, in about 50 ml of 100 mM borate buffer. 2 mg ofMicroperoxidase were weighed out and were dissolved in about 5 ml of 100mM borate buffer. The two reagents were then mixed together in a 200 mlvolumetric flask whose volume was adjusted with borate buffer. The 200ml are placed in a 500 ml flask. 200 ml of borate buffer are then addedthereto again. The reaction mixture, whose final volume was now 400 ml,was homogenized by magnetic stirring and then placed in darkness for atleast 24 hours before use.

[0238] Discs 6 mm in diameter were cut out of a sheet of collagen usinga punch. These discs were then placed in glass Petri dishes, either inaqueous solution or on a 1% agarose gel. Formulae 1 to 4 were applied oneach sample of collagen. For each formula tested, 6 discs were used perdish. Each test formula was applied using a fingerstall so as tosaturate the collagen disc. The Petri dishes were then exposed to UVAradiation (365 nm) of intensity: 10 joules/cm². After the irradiation,the collagen discs were placed in a 96-well plate, in a lightproof box,under a photon-counter camera.

[0239] 150 microlitres of the chemiluminescence reaction mixture werethen distributed into each of the wells involved in the measurement. Atthe same time, the count of the photon camera was triggered. Counting ofthe photons was carried out over a period of 4 minutes.

[0240] The count values obtained were then converted into picomoleequivalents of hydroperoxide (H₂O₂) by linear regression carried outusing a standard range.

[0241] The results are illustrated in FIG. 1. It is observed thatpolyethyleneimine inhibited the formation of collagen peroxides.

We claim:
 1. A cosmetic and/or dermatological composition comprising, ina cosmetically and/or dermatologically acceptable support: at least onenanopigment in said composition, at least one polyamino polymer in saidcomposition selected from: (A) polyalkylenepolyamine polymers selectedfrom: (i) polyalkylenepolyamines; (ii) alkyl derivatives ofpolyalkylenepolyamines; (iii) addition products of alkylcarboxylic acidswith polyalkylenepolyamines; (iv) addition products of ketones andaldehydes with polyalkylenepolyamines; (v) addition products ofisocyanates and isothiocyanates with polyalkylenepolyamines; (vi)addition products of alkylene oxide and polyalkylene oxide blockpolymers with polyalkylenepolyamines; (vii) quaternized derivatives ofpolyalkylenepolyamines; (viii) addition products of a silicone withpolyalkylenepolyamines; (ix) copolymers of dicarboxylic acid and ofpolyalkylenepolyamines; (B) polyvinylimidazoles; (C) polyvinylpyridines;(D) addition products of 1-vinylimidazole monomers of formula (I):

 in which: radicals R independently represent H or a linear or cyclic,saturated or unsaturated C₁-C₆ alkyl radical, n is an integer rangingfrom 1 to 3, with polyalkylenepolyamines (A)(i) to (A)(ix); (E) aminoacid polymers with a basic side chain; and (F) crosslinked derivativesof polymers (A)(i) to (A)(ix), (B), (C), (D) and (E).
 2. A cosmeticand/or dermatological composition according to claim 1, wherein saidpolyalkylenepolyamines comprise from 7 to 20,000 repeating units
 3. Acosmetic and/or dermatological composition according to claim 1, whereinsaid at least one polyamino polymer is selected from polyamino polymerscomprising at least 5% of tertiary amine functions.
 4. A cosmetic and/ordermatological composition according to claim 3, wherein said at leastone polyamino polymer is selected from polyamino polymers comprising atleast 10% of tertiary amine functions.
 5. A cosmetic and/ordermatological composition according to claim 4, wherein said at leastone polyamino polymer is selected from polyamino polymers comprising atleast 20% of tertiary amine functions.
 6. A cosmetic and/ordermatological composition according to claim 1, wherein said at leastone polyamino polymer is selected from: (A) (i) hyperbranchedpolyethyleneimines; (ii) quaternized polyethyleneimine derivatives;(iii) addition products of alkylcarboxylic acids with polyethyleneimine;(iv) addition products of ketones and aldehydes with polyethyleneimine;(v) addition products of isocyanates and isothiocyanates withpolyethyleneimine; (vi) addition products of alkylene oxide andpolyalkylene oxide block polymers with polyethyleneimine; (vii)quaternized polyethyleneimine derivatives; (viii) addition products of asilicone with polyethyleneimine; (ix) copolymers of a dicarboxylic acidand polyethyleneimine; and (B) polyvinylimidazoles.
 7. A cosmetic and/ordermatological composition according to claim 6, wherein said at leastone polyamino polymer is selected from: (A) (i) hyperbranchedpolyethyleneimines; and (A) (vi) addition products of either ethyleneoxide or polyethylene oxide block polymers with polyethyleneimine.
 8. Acosmetic and/or dermatological composition according to claim 7, whereinsaid at least one polyamino polymer is selected from hyperbranchedpolyethyleneimines.
 9. A cosmetic and/or dermatological compositionaccording to claim 1, wherein said at least one nanopigment is selectedfrom metal oxides.
 10. A cosmetic and/or dermatological compositionaccording to claim 9, wherein said at least one nanopigment is selectedfrom titanium oxide, zinc oxide, cerium oxide and zirconium oxide.
 11. Acosmetic and/or dermatological composition according to claim 10,wherein said at least one nanopigment is titanium oxide.
 12. A cosmeticand/or dermatological composition according to claim 1, wherein said atleast one nanopigment is present in an amount ranging from 0.1 to 20% byweight relative to the total weight of said cosmetic and/ordermatological composition.
 13. A cosmetic and/or dermatologicalcomposition according to claim 12, wherein said at least one nanopigmentis present in an amount ranging from 0.25 to 15% by weight relative tothe total weight of said cosmetic and/or dermatological composition. 14.A cosmetic and/or dermatological composition according to claim 1,wherein said at least one polyamino polymer is present in an amountranging from 0.05 to 10% by weight relative to the total weight of saidcosmetic and/or dermatological composition.
 15. A cosmetic and/ordermatological composition according to claim 14, wherein said at leastone polyamino polymer is present in an amount ranging from 0.5 to 5% byweight relative to the total weight of said cosmetic and/ordermatological composition.
 16. A cosmetic and/or dermatologicalcomposition according to claim 1, wherein said cosmetic and/ordermatological composition further comprises at least onephoto-oxidizable fatty substance.
 17. A cosmetic and/or dermatologicalcomposition according to claim 16, wherein said at least onephoto-oxidizable fatty substance is selected from photo-oxidizable fattysubstances with iodine values ranging from 5 to
 200. 18. A cosmeticand/or dermatological composition according to claim 1, containing afatty phase including at least one oil and wherein the degree ofunsaturation (C) of the fatty phase of said cosmetic and/ordermatological composition, defined by the formula:$C = {\sum\limits_{i = 1}^{n}\quad {\left\lbrack {V.I.} \right\rbrack i*\left\lbrack {T.H} \right\rbrack i}}$

in which [V.I.]i represents the iodine value of the oil i, and [T.H.]irepresents the weight percentage relative to the total weight of saidfatty phase, ranges from 2.5 to
 4000. 19. A cosmetic and/ordermatological composition according to claim 18, wherein said degree ofunsaturation (C) of the fatty phase of said composition ranges from 50to
 4000. 20. A cosmetic and/or dermatological composition according toclaim 16, wherein said at least one photo-oxidizable fatty substance ispresent in an amount ranging from 0.5 to 60% by weight relative to thetotal weight of said cosmetic and/or dermatological composition.
 21. Acosmetic and/or dermatological composition according to claim 1, whereinsaid cosmetic and/or dermatological composition further comprises atleast one protein or protein derivative.
 22. A cosmetic and/ordermatological composition according to claim 1, wherein saidcomposition further comprises at least one oil.
 23. A cosmetic and/ordermatological composition according to claim 22, wherein said at leastone oil is selected from apricot oil, sweet almond oil, groundnut oil,avocado oil, candlenut oil, borage oil, camellia oil, false flax oil,safflower oil, blackcurrant oil, cereal oil, chayote oil, coconut oil,rapeseed oil, coriander oil, cotton oil, cumin oil, cynara oil, eveningprimrose oil, perilla oil, cod liver oil, corn germ oil, jojoba oil,kiwi oil, lanolin oil, lychee oil, linseed oil, longan oil, mango oil,hazelnut oil, olive oil, palm oil, passionflower oil, grapeseed oil,cluster pine oil, Italian stone pine oil, pistachio oil, musk rose oil,sesame oil, shorea oil (floor grease), soybean oil, rice bran oil,turtle oil, sunflower oil, whale oil, tea oil, karite butter and vitaminF triglycerides.
 24. A cosmetic and/or dermatological compositionaccording to claim 1, wherein said composition further comprises atleast one metal-complexing agent.
 25. A cosmetic and/or dermatologicalcomposition according to claim 21, wherein said at least onemetal-complexing agent is selected from3-ethylenediaminetetra(methylenephosphonic acid),diethylenetriaminepenta(methylenephosphonic acid) anddiethylenetriaminepentaacetic acid, and sodium salts thereof.
 26. Acosmetic and/or dermatological composition according to claim 25,wherein said at least one metal-complexing agent is present in an amountranging from 0.005% to 0.1% by weight relative to the total weight ofsaid cosmetic and/or dermatological composition.
 27. A cosmetic and/ordermatological composition according to claim 1, wherein said cosmeticand/or dermatological composition is in the form of an oil-in-water orwater-in-oil emulsion, a solution, a gel, a vesicular dispersion, asolid, a foam, a mousse, or a spray.
 28. A cosmetic and/ordermatological composition according to claim 1, wherein said cosmeticand/or dermatological composition further comprises at least oneconventional cosmetic adjuvant.
 29. A method of treating the signs ofageing of the skin or the hair comprising applying at least onedermatological composition according to claim 1 to said skin or hair.30. A method according to claim 29, wherein said signs of ageing areinduced by photo-peroxidation.
 31. A method according to claim 30,wherein said signs of ageing are induced by photo-peroxidation ofsqualene or collagen.
 32. A topical cosmetic treatment process forcombatting or preventing signs of ageing comprising: topically applyingat least one cosmetic composition according to claim 1 to the skin,scalp, or hair.
 33. A cosmetic or dermatological composition forprotecting the human epidermis or the hair against ultraviolet rayscomprising at least one nanopigment in said composition and at least onepolyamino polymer in said composition as defined in claim
 1. 34. Acosmetic or dermatolgocial composition according to claim 33 whereinsaid composition is an antisun composition or a make-up product.
 35. Acosmetic or dermatolgocial composition for combatting or preventinglight-induced irritation, inflammation, immunosuppression or acnecomprising comprising at least one nanopigment in said composition andat least one polyamino polymer in said composition as defined inclaim
 1. 36. A process for conserving cosmetic, pharmaceutical,veterinary or agrifood compositions containing at least onephoto-oxidizable lipid, protein or protein derivative comprisingincorporating in said composition at least one polyamino polymerselected from: (A) polyalkylenepolyamine polymers selected from: (i)polyalkylenepolyamines; (ii) alkyl derivatives ofpolyalkylenepolyamines; (iii) addition products of alkylcarboxylic acidswith polyalkylenepolyamines; (iv) addition products of ketones andaldehydes with polyalkylenepolyamines; (v) addition products ofisocyanates and isothiocyanates with polyalkylenepolyamines; (vi)addition products of alkylene oxide and polyalkylene oxide blockpolymers with polyalkylenepolyamines; (vii) quaternized derivatives ofpolyalkylenepolyamines; (viii) addition products of a silicone withpolyalkylenepolyamines; (ix) copolymers of dicarboxylic acid andpolyalkylenepolyamines; (B) polyvinylimidazoles; (C) polyvinylpyridines;(D) addition products of 1-vinylimidazole monomers of formula (I):

in which: radicals R independently represent H or a linear or cyclic,saturated or unsaturated C₁-C₆ alkyl radical, n is an integer rangingfrom 1 to 3, with polyalkylenepolyamines (A)(i) to (A)(ix); (E) aminoacid polymers with a basic side chain; and (F) crosslinked derivativesof polymers (A)(i) to (A)(ix), (B), (C), (D) and (E).
 37. An antioxidantcomposition comprising at least one polyamino polymer in saidcomposition selected from: (A) polyalkylenepolyamine polymers selectedfrom: (i) polyalkylenepolyamines; (ii) alkyl derivatives ofpolyalkylenepolyamines; (iii) addition products of alkylcarboxylic acidswith polyalkylenepolyamines; (iv) addition products of ketones andaldehydes with polyalkylenepolyamines; (v) addition products ofisocyanates and isothiocyanates with polyalkylenepolyamines; (vi)addition products of alkylene oxide and polyalkylene oxide blockpolymers with polyalkylenepolyamines; (vii) quaternized derivatives ofpolyalkylenepolyamines; (viii) addition products of a silicone withpolyalkylenepolyamines; (ix) copolymers of dicarboxylic acid andpolyalkylenepolyamines; (B) polyvinylimidazoles; (C) polyvinylpyridines;(D) addition products of 1-vinylimidazole monomers of formula (I):

in which the radicals R independently represent H or a linear or cyclic,saturated or unsaturated C₁-C₆ alkyl radical, n is an integer rangingfrom 1 to 3, with polyalkylenepolyamines (A)(i) to (A)(ix); (E) aminoacid polymers with a basic side chain; and (F) crosslinked derivativesof the polymers (A)(i) to (A)(ix), (B), (C), (D) and (E).
 38. A methodfor providing antioxidation properties to a substrate or compositionsubject to oxidation comprising the step of contacting said substrate orcomposition with at least one polyamino polymer selected from: (A)polyalkylenepolyamine polymers selected from: (i)polyalkylenepolyamines; (ii) alkyl derivatives ofpolyalkylenepolyamines; (iii) addition products of alkylcarboxylic acidswith polyalkylenepolyamines; (iv) addition products of ketones andaldehydes with polyalkylenepolyamines; (v) addition products ofisocyanates and isothiocyanates with polyalkylenepolyamines; (vi)addition products of alkylene oxide and polyalkylene oxide blockpolymers with polyalkylenepolyamines; (vii) quaternized derivatives ofpolyalkylenepolyamines; (viii) addition products of a silicone withpolyalkylenepolyamines; (ix) copolymers of dicarboxylic acid andpolyalkylenepolyamines; (B) polyvinylimidazoles; (C) polyvinylpyridines;(D) addition products of 1-vinylimidazole monomers of formula (I):

in which the radicals R independently represent H or a linear or cyclic,saturated or unsaturated C₁-C₆ alkyl radical, n is an integer rangingfrom 1 to 3, with polyalkylenepolyamines (A)(i) to (A)(ix); (E) aminoacid polymers with a basic side chain; and (F) crosslinked derivativesof the polymers (A)(i) to (A)(ix), (B), (C), (D) and (E).
 39. A methodaccording to claim 38, wherein said substrate is human epidermis orhair.
 40. A method for curative or preventive treatment of irritation,inflammation, immunosuppression or acne comprising applying at least onecosmetic and/or dermatological composition according to claim 1 to asubstrate or composition in need of such treatment.
 41. A methodaccording to claim 40, wherein said substrate is human epidermis orhair.
 42. A method for inhibiting the peroxidation of lipids induced byUV radiation comprising the step of contacting said lipids with at leastone cosmetic and/or dermatological composition according to claim
 1. 43.A method for inhibiting the peroxidation of proteins and proteinderivatives induced by UV radiation comprising applying to said proteinsand protein derivatives at least one cosmetic and/or dermatologicalcomposition according to claim
 1. 44. A process for conserving acosmetic, an agrifood and/or a pharmaceutical composition comprising atleast one photo-oxidizable lipid or protein or protein derivative,comprising including in said composition at least one polyamino polymeraccording to claim 1.